Gluconic acid salts of certain oxyalkylated amine-modified thermoplastic phenol-aldehyde resins, and method of making same



United States GLUCONIC ACID SALTS OF CERTAIN OXYALKYL- ATED AMINE MODIFIED THERMOPLASTIC PHENOL-ALDEHYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, Mo., assignor to Petrolite Corporation, Wilmington, Del, a corporation of Delaware 13 Claims. (Cl. 260-53) The present invention is a continuation-in-part of my five co-pending applications, Serial No. 288,746, filed May 19, 1952, now abandoned; Serial No. 296,087, filed June 27, 1952, now U. S. Patent 2,679,488; Serial No. 301,807, filed July 30, 1952, Patent No. 2,743,256; Serial No. 310,555, filed September 19, 1952, Patent No. 2,695,891, now U. S. Patent 2,695,891; Serial No. 329,486, filed January 2, 1953; and a division of my co-pending application Serial No. 333,390, filed January 26, 1953, Patent No. 2,771,449.

My invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. My invention is also concerned with the application of such chemical products or compounds in various other arts and industries as Well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

My aforementioned co-pending application, Serial No. 301,807, filed July 30, 1952, is concerned with the process of first condensing certain phenolaldehyde resins, therein described in detail, with certain cyclic amidines, therein described in detail, and formaldehyde, which condensation is followed by oxyalkylation with certain monoepoxides, also thereindescribed in detail.

The present invention is concerned with the aforementioned oxyalkylated amino resin condensate in the form of a gluconic acid salt, i. e., a form in which part or all the basic nitrogen atoms are neutralized with gluconic acid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending application, Serial No. 310,555, filed September 19, 1952, is concerned with a process for breaking petroleum emulsions of the waterinoil type characterized by subjecting the emulsion to the action of a demulsifier including the amine resin condensates described in the aforementioned application Serial No. 301,807.

Needless to say, all that is required is to prepare the oxyalkylated amine resin condensates in the manner described in the two aforementioned co-pending applications, and then neutralize with gluconic acid which, for practical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described productsgoes for purpose of resolution of petroleum emulsions of the Water-in-oil type, I particularly prefer to use the gluconic acid salt of those members which have sufficient hydrophile character to meet at least the test as set forth in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

atent O The present invention involves the surface-activity of the gluconic acid salts, i. e., either where only one basic amino nitrogen atom is neutralized or where all basic I amino nitrogen atoms are neutralized. Such gluconie acid salts may not necessarily be Xylene-soluble. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a watersoluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of Xylene in the emulsification test includes such obvious variant.

For convenience, what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the general structure of the amine-modified resins which after oxyalkylation are converted to the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 3 is concerned with suitable basic amidines which may be employed in the preparation of the herein described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the cyclic amidine, and formaldehyde to produce specific products or compounds which are then subjected to oxyalkylation; I

Part 5 is concerned with the oxyalkylation of the products described in Part 4 preceding;

Part 6 is concerned with the conversion of the basic oxyalkylated derivatives described in Part 5, preceding, in the corresponding salt of gluconic acid;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products in the form of gluconic acid salts; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type. This part islimited also to the use of the gluconic acid salts.

For reasons which are obvious, particularly for convenience and ease of comparison, the various parts are in substantially verbatim form as they appear in one or more of the aforementioned co-pending applications, to wit, Serial Nos. 288,746, 296,087, 301,807, 310,555, and 329,486. For example, Parts 1, 2, 3 and 4 are substantially as they appear in co-pending application, Serial No. 329,486, filed January 2, 1953; Part5 is substantially the same as it appears in aforementioned co-pending applica tion, Serial No. 301,807, filed July 30, 1952, and Serial No. 310,555, filed September 19, 1952. Part 6 corresponds approximately to what appears in Serial No. 329,486, filed January 2, 1953.

PART 1 The compounds herein described and particularly useful as demulsifying agents are gluconic acid salts of heat-stable and oxyalkylation-susceptible resinous condensation products obtained by oxyallcylating the amine resin condensates described in applications Serial Nos. 288,746 and 296,087 to which reference is made for a discussion of the general structure of such resins.

These resins may be exemplified by an idealized formula which may, in part, be an over-simplification in an eifort to present certain resin structure. Such formula would be the following:

H H H H R R R in which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it is shown as being de rived from formaldehyde although obviously other aldehydes are equally satisfactory. The amine residue in the above structure is derived from either a substituted imidazoline or a substituted tetrahydropyrimidine as previously specified and may be indicated thus:

in which HN represents a reactive secondary amino group and two occurrences of R represent the remainder of the molecule. Stated another way, what has been depicted in the above formula is an over-simplification as far as the ring compound is concerned which is obvious by reference to a more elaborate formula depicting the actual structure of typical members of the group, such as:

N- Hi 0 H3. 0

IIT- 0 H2 CizH4.NH. C 2H4.NH. C mHss 2-methyl, l-hexade cylamino ethyIamino ethylimidaz oline .Z-heptadecyl,l-methylaminoethyl tetrahydropyrimidine The introduction of two such ring compound radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counterbalancing hydrophobe effect or one in which the hydrophobe effect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect. In such instances where there are hydroxyl groups present, needless to say there is a further hydrophile effect introduced.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which are reactive to formaldehyde, i. e., they are difunctional from the standpoint of methylolforming reactions. As is well known, although one may start with difunctional phenols, and depending on the procedure employed, one may obtain cross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a tiifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2.

Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, shifts from an ortho position to a meta position, or from a para position to a meta posi tion. For instance, in the case of phenol-aldehyde varnish resins, one can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction, with formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

The resins herein employed are soluble in a non oxygenated hydrocarbon solvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the free base or the salt, do not go over to the insoluble stage on heating. The condensation product obtained according to the present invention is heat stable and, in fact, one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularly when employed as a reactant for preparation of derivatives, is still important from the standpoint of manufacture of the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing of a temperature above the boiling point of water. As a matter of fact, all the examples included subsequently employ temperatures going up to to C.

What is said above deserves further amplification at this point for the reason that it may shorten what is said subsequently in regard to the production of the herein described condensation products. Since formaldehyde generally is employed economically in an aqueous phase (30% to 40% solution, for example) it is necessary to have manufacturing procedure which will allow reactions to take place at the interface of the two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine will dissolve in one phase or the other. Although reactions of the kind herein described will begin at least at comparatively low temperatures, for instance, 30 C., 40 C., or 50 C., yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one can add an oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce'a homogeneous phase. If this latter procedure is employed in preparing the herein described condensations it is purely a matter of convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order irlwhich the reactants are added, cornmingled or reacted. The procedure has been referred to as a condensation process for obvious reasons; As pointed out elsewhere it is my preference to dissolve the resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. -I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immaterial if both types of compounds were formed which reacted with each other with the evolution of a mole of formaldehyde available for further reaction. Furthermore, a reaction could take place in which three different molecules are simultaneously involved although, for theoretical reasons, that is less likely. What is said herein in this respect is simply by way of explanation to avoid any limitation in regard to the appended claims.

PART 2 .mated in an idealized form by the formula on on OH H l 11 o o H H R R n R In the above formula 11 represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent generally an .alkyl radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote and Kaiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

R R n R The basic amine may be designated thus:

subject to what has been said previously as to the presence of a substituted imidazoline or a substituted tetrahydropyrrmidine radical having at least one basic secondary amine radical present and that the ring compound, or rather the two occurrences of R jointly with n, be free from a primary amine radical. However, if one attempts to incorporate into the formula RI HN/ a structure such as a substituted imidazoline or substituted tetrahydropyrimidine such as the following:

/N-CH2 Ot1Ha5-C N-CH1 GsHiOH then one becomes involved in added difficulties in presenting an overall picture. Thus, for sake of simplicity the ring compound having the reactive secondary amino group will be depicted as R! subject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

OH OH As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldhyde. The resin unit may be exemplified thus:

R R n R having neither acid nor basic properties in the ordinary r sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other Words, if prepared byusing a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base. is used as a catalyst it is preferable that the base be neutralized although I have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be :as small as a 200th of a percent and as much as a few lths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating4 phenolic nuclei Will have some trimer and pentamer present. Thus, the molecular Weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table:

TABLE I Moi. wt EX Position R of resin ample R of R derived n molecule number 0m (based on n+2) Phony] Para. Formal- 3. 5 992. 5

Tertiary butyl .d0.- 3. 5 822. 5 Secondary butyl Ortho. 3. 5 882. 5 Cyclo-hexyl. Para 3. 5 1, 025. 5 Tertiary amyl ...do. 3. 5 959. 5 Mixed secondary 0rtho. 3. 5 S05. 5

and tertiary amyl.

3. 5 805. 5 3. 5 1, 036. 5 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 o. 3. 5 1, 498. 5 Acetalde- 3. 6 945. 5

hyde. d0 3. 5 1,022. 5 ..do 3.5 1,330.5 Butyn- 3. 5 1,071. 5

aldehyde do 3. 5 1,148.5 d0 3.5 1, 456.5 Propion- 3. 5 1, G08. 5 aldehyde. Tertiary amyl 3. 5 1, 085. 5 Nonyl 3. 5 1, 393. 5 Tertiary butyl 4. 2 996. 6

Tertiary amyl 4. 2 1, 083. 4 Nonyl 4. 2' 1, 430. 6 Tertiary butyl 4. 8 1, 094. 4 Tertiary omyl 4. 8 1, 189. 6 4. S 1, 570. 4 1. 5 604.0 1. 5 646. 0 l. 5 653.0 1. 5 688. 0

2.0 692. 0 Hexyl 2. 0 748.0 Oyelo-hexyl 2. 0 740. 0

PART 3 The expression cyclic amidines is employed in its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms may be substituted. The nitrogen atom of the ring involving two monovalent linkages may be substituted. Needless to say, these compounds include mem- 3 bers in which the substituents also mayhav'e one or'm'or'e nitrogen atoms, either in the form of amino nitrogen atomsor in the form of acylated nitrogen'atoms. Reference is made to applications SerialNos. 288,746 and 296,087 for a discussion of the cyclic amidines which may be used in producing the compounds used in accordance with the present invention.

Examples selected include the following:

H 2-undecylim1dazoline N- C H III-C H: H Z-heptadecylimidazolim CaHs.NH. OizHzs 'l-dodecylaminopropylimidazoline N- 0 Ha H. C

CgH4.NH.C2H4O CH.C11H:5 1(stearoy1oxyethyl) aminoethylimidazoline N-CHz H. C

CQHLNH. C2H4NHO G.C17Has 1 -stearamidoethylamiuoethylimidazoline N-GH2 H. C

NG H2 CrHt-IIT. C2H4.NHOC.CH3

1- (n-dodecyl) -acetamidoethy1aminoethylimidazoline NO HC Ha Ci1HstC NGH-C Ha 2-heptadecy1,4,5-dimethylimidazoline N -C Hg IIl-C Hz CsH z.NH. CrzHzs l-dodecylaminohexylimidazoline %N- G H; H. C

CflHH-NH. C2134. 0 (3151135 l-stearoyloxyethylaminohexylimldazoline N C H:

4-111ethyl,2-dodecyl,l-methylaminoethylaminoethyl tetrahydropyrimidine CuHzs- As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula:

As to compounds having a tertiary amine radical, it is obvious that one can employ derivatives of polyamines in which the terminal groups are unsymmetrically alkylated. Initial polyamines of this type are illustrated by the following formula:

in which R represents a small alkyl radical such as methyl, ethyl, propyl, etc., and n represents a small whole number greater than unity such as 2, 3 or 4.

Ring compounds, such as substituted imidazolines, may be reacted with a substantial amount of alkylene oxide as noted and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkylating agent such as dimethyl sulfate, benzyl chloride, a low molal ester of a sulfonic acid, an alkyl bromide, etc.

Other suitable means may be employed to eliminate a terminal primary amino radical. If there is additionally a basic secondary amino radical present then the primary if) amino radical can be subjected to acyla'tion notwithstanding the fact that the surviving amino group has no significant basicity. As a rule acylatio'n takes place at the terminal primary amino group rather than at the 'secondary amino group, thus one can employ a compound such as /NCH: CI7HB5 C/ N C H:

C2H4.NH.C:H4.NH2 2-heptadecy1,l-diethylenediaminoimidazoline and subject it to acylation so as to obtain, for example, acetylated Z-heptadecyl,1-diethylenediaminoimidazoline of the following structure:

Similarly, a compound having no basic secondary amino radical but a basic primary amino radical can.

, be reacted with a mole of an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectly satisfactory reactant for the herein described? This can be illustrated in the:

condensation procedure. following manner by a compound such as ide, for example, to produce the hydroxy ethyl derivative of Z-heptadecyl,l-amino-ethylimidazoline, which can be illustrated by the following formula:

. N-C'Hr PART 4 The. products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself. The condensation of the resin, cyclic amidine and formaldehyde is described in detail in applications Serial Nos. 288,746 and 296,087, and reference is made to those applications for a discussion of the factors involved.

Little more need be said 'as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example .1 b

The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiarybutylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

12 was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogenericmixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately hours. In other examples, it varied from as little as 24 hours up to approximately 38 hours. The time can be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a farily low temperature (30 to for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the Water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usualy the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE II Strength of Reae- Reae- Max. Ex Resin Amt, Amine used Amt. of formaldehyde Solvent used tion tion distill. No d gl's, amine, soln. and amt. and amt. temp., time mp,

grams 0. (hrs) C.

612 37%, 162 g.-. 30 148 306 37%, 81 g l. 24 145 306 do 28 150 281 30%, 100 28 148 281 do 30 148 281 37%, 81 g 26 146 394 do 26 147 394 ..do 26 146 394 -.-.-d0 38 150 379 30%, 100 g--. 36 149 379 d0 24 142 379 do 26 145 395 38%, 81 g 28 146 395 37%, 81g Xylene, 450 23-30 27 150 395 .....do Xylene, 550 h... 20-24 29 147 99 d0 Xylene, 440 g 20 21 30 148 99 do Xylene, 480 g 21-26 32 146 Xylene, 600 g 21-23 26 147 Xylene, 509 a 21-32 29 150 "undo... 21-30 32 150 Xylene, 550 21-23 37 150 Xylene, 440 20-22 30 L 126 d0 Xylene, 600 g. 2025 36 140 126 30%, 50 g Xylene, 400 g. 20-24 32 152 882 grams of the resin identified as 2a, preceding, were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximatcly 35 C. and 612 grams of Z-oleylimidazoline, previously shown in a structural formula as ring compound (3), Were added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 /2 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction.- After the water was eliminated part of the xylene The amine numbers referred to are the ring compounds identified previously by number in Part 3.

PART 5 In preparing oxyalkylated derivatives of products of the kind which appear as examples in Part 3, I have found it particularly advantageous to use laboratory equipment which permits continuous oxypropylation and oxyethylation. More specific reference will be made to treatment with glycide subsequently in the text. The oxyethylation step is, of course, the same as the oxypropylation step insofar that two low boiling liquids are handled in each instance. What immediately follows refers to oxyethylation and it is understood that oxypropylation can be handled conveniently in exactly the same manner. The oxyalkylation of the amine resin condensates is carried out by procedures which are commonly used for the oxyalkylation of oxyalkylation susceptible materials. The factors to be considered are discussed in some detail in applications Serial Nos. 301,807 and 310,555 and reference is made to those applications one-half hours.

Example The oxyalkylation-susceptible compound employed is the one previously described and designated as Example 1b. Condensate 1b was in turn obtained from 2-oleylimidazoline and the resin previously identified as Example 2a. Reference to Table I shows that this particular resin is obtained from paratertiarybutylphenol and formaldehyde. 15.18 pounds of this resin condensate were dis solved in 6 pounds of solvent (xylene) along with 1.0 pounds of finely powdered caustic soda as a catalyst. Adjustment was made in the autoclave to operate at a temperature of approximately 125 C. to 135 C., and at a pressure of about 20 to 25 pounds. In some subsequent examples pressures up to 35 pounds were employed.

The time regulator was set so as to inject the ethylene oxide in approximately three-quarters of an hour and then continue stirring for minutes or longer, a total time of one hour. The reaction went readily, and, as a matter of fact, the oxide was taken up almost immediately. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to excellent agitation and also to the comparatively high concentration of catalyst. The amount of ethylene oxide introduced was equal in weight to the initial condensation product, to wit, 15.18 pounds. This represented a molal ratio of 34.5 moles of ethylene oxide per mole of condensate.

The theoretical molecular weight at the end of the reaction period was 3036. A comparativelysmall sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data, or subsequent data, or in the data presented in tabular form in subsequent Tables III and IV.

The size of the autoclave employed was 25 gallons. In innumerable comparable oxyalkylations I have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example This example simply illustrates the further oxyalkylation of Example 10, preceding. As previously stated, the oxyalkylation-susceptible compound, to wit, Example 15, present at the beginning of the stage was obviously the same as at the end of the prior stage (Example 1c), to wit, 15.18 potmds. The amount of oxide present in the initial step was 15.18 pounds, the amount of catalyst remained the same, to wit, 1.0 pounds, and the amount of solvent remained the same. The amount of oxide added was another 15.18pounds, all addition of oxide in these various stages being based on the addition of this particular amount. Thus, at the end of the oxyethylation step the amount of oxide added was a total of 30.36 pounds and the molal ratio of ethylene oxide to resin condensate was 69.0 to 1.0. The theoretical molecular weight was 3348.

The maximum temperature during the operation was 125 C. to 130 C. The maximum pressure was in the range of 20 to pounds. The time period was one and Example The oxyalkylation proceeded in the same manner described in Examples 10 and 2c. There was no added solvent and no added catalyst. The oxide added was 15.18 pounds and the total oxide at the end of the oxyethylation step was 45.54 pounds. The molal ratio of oxide to condensate was 103.5 to 1. Conditions as far as temperature and pressure and time were concerned were all the same as in Example 10 and 2c. The time period was somewhat longer than in previous examples, to wit, 3 hours.

Example 40 Example 50 The oxyethylation continued with the introduction of another 15.18 pounds of ethylene oxide. No more solvent was introduced but .3 pound caustic soda was added.

The theoretical molecular weight at the end of the agitation period was 9108, and the molal ratio of oxide to resin condensate was 172.5 to 1. The time period, however, dropped to 3 hours. Operating temperature and pressure remained the same as in the previous example.

Example 6c The same procedure was followed as in the previous examples. The amount of oxide added .was another 15.18 pounds, bringing the total oxide introduced to 91.08 pounds. The temperature and pressure during this period were the same as before. There was no added solvent. The time period was 3% hours. Molal ration of oxide to resin condensate was 207.0 to one.

Example 70 The same procedure was followed as in the previous six examples without the addition of more caustic or more solvent. The total amount of oxide introduced at the end of the period was 106.26 pounds. The theoretical molecular weight at the end of the oxyalkylation period was 12,144. The time required for the oxyethylation was a bit longer than in the previous step, to wit, 4 hours.

Example This was the final oxyethylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 121.44 pounds. The theoretical molecular weight was 13,662. The molal ratio of oxide to resin condensate was 276.0 to one. Conditions as far as temperature and pressure were concerned were the same as in the previous examples and the time required for oxyethylation was 4 hours.

The same procedure as described in the previous examples was employed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables III and IV, V and VI.

In substantially every case a 25-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables III and IV, it will be noted that compounds 10 through 406 were obtained by the use of ethylene oxide, whereas 410 through 800 were obtained by the use of propylene oxide alone.

Thus, in reference to Table III it is to be noted as follows:

the first column.

The'identity of the oxyalkylation-susceptible compound, to wit, the resin, condensate, is indicated in the second column.

The amount of condensate is shown in the third column.

Assuming that ethylene oxide'alone is employed, as happens to be the case in Examples 10 through 400, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent employed.

The 8th column can be ignored where a single oxide was employed.

The 9th column shows the theoretical molecular weight at the end of the oxyalkylation period.

The 10th column states the amount of condensate present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin condensate in column 10 coincides with the figure in column 3.

Column 11 shows the amount of ethylene oxide employed in the reaction mass at the end of the particular period.

Column 12 can be ignored insofar that no propylene oxide was employed.

Column 13 shows the catalyst at the end of the reaction period.

Column 14 shows the amount of solvent at the end of the reaction period.

Column 15 shows the molal ratio of ethylene oxide I to condensate.

Column 16 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table VI. It is to be noted that the first column refers to Examples 10, 20, 30, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present, with several volumes of water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring to Table IV, Examples 410 through 800 are the counterparts of Examples 10 through 400, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, four columns are blank, to wit, columns 4, 8, 11 and 15.

Reference is now made to Table V. It is to be noted these compounds are designated by d numbers, 1d 2d, 3d, etc, through and including 320.. They are derived, in turn, from compounds in the c series, for example 36c, 40c, 54c, and 76c. These compounds involve the use of both ethylene oxide and propylene oxide. Since compounds le through 400 were obtained by the use of ethylene oxide, it is obvious that those obtained from 36c and 49c, involve the use of ethylene oxide first, and propylene oxide afterward. inversely, those compounds obtained from 540 and 760 obviously come from a prior ries in. which propylene oxide was used first.

In the preparation of this series indicated by the small letter d, as id, 2:], 3d, etc. the initial c series such as 360, 405', 54c, and 760, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further may have been theease in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, to wit, propylene oxide in 1d through 16d, and ethylene oxide in 17d through 32d, inclusive.

In examining the table beginning with 10!, it Will be noted that the initial product, i. e., 360, consisted of the reaction product involving 15.18 pounds of the resin condensate, 22.27 pounds of ethylene oxide, 1.0 pound of caustic soda, and 6.0 pounds of the solvent.

It is to be noted that reference to the catalyst in Table V 7 refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.'

In this series, it will be noted that the theoretical molecular weights are given prior to the oxyalkylation step and after the oxyalkylation step, although the value at the end of one step is the value at the beginning of the next step, except obviously at the very start the value depends on the theoretical molecular weight at the end of the initial oxyalkylation step; i. e., oxyethylation for 1d through 16d, and oxypropylation for 17d through 32d.

It will be noted also that under the molal ratio the values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table VI.

The products resulting from these procedures may con tain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no attempt to selectively add one and then the other, or any other variant;

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorizecl by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se. are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more diflicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE VI-Oontinued Solubility Time,

1). s. 1. hrs.

Xylene Kerosene PART 6 the kind previously described into the corresponding salt of gluconic acid is a simple operation since it is nothing more nor less than neutralization. The condensate invariably contains two basic nitrogen atoms. One can neutralize either one or both nitrogen atoms.

Another factor which requires some consideration would be the presence of basic catalysts which were used during the oxyalkylation process. Actual tests indicate that the basicity appears to be somewhat less than would be expected, particularly in examples in which oxyalkyla- 75 for all practical purposes, at least at a temperature slightly Insoluble.

Do. Disperslblo.

Solu

D o. Insoluble.

Do. Dlsperslble. Soluble.

Do. Insoluble.

Do. Disperslble. Solo 9.

o. Dlspersible. Solu tion is comparatively high. The usual procedure has been to add enough gluconic acid to convert the product into the salt as predetermined and then note whether or not the product showed any marked alkalinity. If so, slightly more gluconic acid was added until the product was either just barely acid or just very moderately alkaline.

0 For sake of clarity this added amount of gluconic acid, if

required, is ignored in subsequent Table VIII.

Gluconic acid is available as a 50% solution. Dehydration causes decomposition. This is not true of the salts,

or at least, the salts of the herein described oxyalkylated" condensates. Such salts appear to be stable, or stable- "23 above the boiling point of water and perhaps at a temperature as high as 150 C. or thereabouts.

As has been pointed out previously the present application is a continuation-in-part of certain co-pending applications and reference is made to aforementioned copending application, Serial No. 329,486, filed January 2, 1953. The co-pending application, Serial No. 329,486, filed January 2, 1953, described the neutralization of the non-oxyalkylated condensate.

Reference is now made to Table VII which, in essence, is substantially the same as much of the data in Table II but includes additional calculations showing the amount of gluconic acid (50%) required to neutralize a certain amount of condensate; for instance, compare Example 1e in Table VII, with Example 1b in Table II. In any event, since there were available various oxyalkylated derivatives of condensate lb and 5b, these particular oxyalkylated derivatives were used for the purpose of illustrating salt formation, all of which is illustrated in Table VIII.

Briefly stated, referring to Example 12, in Table VII it is to be noted that 1518 grams of the nonoxyalkylated condensate required 1480 grams of 50% gluconic acid for neutralization. Reference to Table VIII shows that 1518 grams of the condensate Example 112, when converted into the oxyalkylated derivative as obtained from 20, were equivalent to 5180 grams. Therefore, 5180 grains were selected as the appropriate amount of oxyalkylated material for neutralization simply for the reason that calculation was eliminated.

The oxyalkylated condensate generally is a liquid and, as a rule, contains a comparatively small amount of solvent. Note the examples in Table VIII. The solvent happened to be xylene in this instance but could have been benzene, aromatic petroleum solvent, or the like. Needless to say, the solvent could have been removed from the oxyalkylated derivative by use of vacuum distillation and this is particularly true if benzene happened to be the solvent. The product obtained from oxyalkylation invariably is lighter than the initial material for the reason that the condensate is dark colored and oxyalkylation simply dilutes the color. In other words, the product may be almost white, pale straw color, or an amber shade with a reddish tint.

The product either before or after neutralization can 1 be bleached with filtering clays, charcoals, etc. The procedure generally is, as a matter of convenience, to form the salt and then dilute with a solvent if desired, using such solvent as xylene or a mixture of two-thirds xylene and one-third ethyl alcohol or isopropyl alcohol, to give approximately a 50% solution. If there happened to be any precipitate the solution is filtered. If desired, the product prior to dilution could be rendered anhydrous simply by adding benzene and subjecting the mixture to reflux action under a condensate or a phase-separating trap. If there happened to be any tendency for the prod uct to separate then the solvents having hydrotropic properties, such as the diethylether of ethyleneglycol, or the like, are used.

The salt formation is merely a matter of agitation at room temperature, or at a somewhat higher tempera ture if desired, particularly in a reflux condenser. Usually agitation is continued for an hour but actually neutralization may be a matter of minutes. In some instances after salt formation is complete and the product is diluted to approximately 50%, l have permitted the solution to stand for about 6 to 72 hours. Sometimes, de pending on composition, there is a separation of an aqueous phase or a small amount of salt-like material. On a laboratory scale the procedure is conducted in a separatory funnel. If there is separation of an aqueous phase, or any other undesirable material, at the bottom of the separatory funnel it is merely discarded. The salt form, of course, can be bleached in the same manner as previously described for the oxyalkylated derivative. Usually the color of the salt is practically the same as the oxyalkylated derivative. For various commercial purposes in. which the product is used there is no justification for the added cost of decolorization. The saltform can be dehydrated or rendered solvent-free by the usual procedure, i. e., vacuum distillation, after the use of a phaseseparating trap.

The product as prepared, without attempting to decoorize. eliminate any residual catalyst in the form of a. salt, and without any particular effort to obtain absolute neutrality or the equivalent, is more satisfactory for a number of purposes where the material is useful, such as a demulsifier for petroleum emulsions of the waterin-oil type, or oil-in-water type; for the prevention of corrosion of metallic surfaces, especially ferrous surfaces; or as an asphalt additive for anti-stripping purposes.

The condensates prior to oxyalkylation may be solids but are generally viscous liquids or liquids which are almost solid or tacky. Oxyalkylation reduces such materials to viscous liquids or thin liquids comparable to polyglycols, of course depending primarily on the amount of alkylene oxide added. After neutralization the physical characteristics of the products are about the same and in the majority of cases are liquids. Needless to say, if a solvent were added, even if the material were solid initially, it would be converted into a liquid form.

In light of what has been said and. the simplicity of salt formation it does not appear that any illustration is required. However, previous reference has been made to Table VIII. The first example in Table VIII is Example 17. The following is more specific data in regard to Example If.

Example If The salt was made from oxyalkylated derivative 20. Oxyalkylated derivative 2c was made from condensate 1b; condensate 1b was made from resin example 2:; and amine 3 which was 2-oleylirnidazoline, all of which has been previously described. The manufacture of the condensate required 612 grams of the amine and 162 grams of formaldehyde. The weight of the condensate on a solvent-free basis was 151.8 grams. This represented approximately 53 grams of basic nitrogen subject to what is said shortly hereafter.

Referring to Table VIII it will be noted that 15.18 pounds of the condensate were combined with 30.36 pounds of ethylene oxide and 6 pounds of solvent. In any event, 4135 grams of the oxyalkylated derivative 20 were placed in a laboratory device which, although made of metal, was the equivalent of a 'separatory funnel. To this there was added 1480 grams of gluconic acid and the mixture stirred vigorously for 2 hours, and then allowed to stand at room temperature for approximately 6 hours.

alkylated product may vary a little from the exact amount stated but, in any event these two factors explain the slight variation which appears in respect to the amount of gluconic acid used to neutralize the amine condensate. This same factor is noted in my co-pending application, Serial No. 329,486, filed January 2, 1953.

A number of other examples are included in Table VIII. For convenience, Table VII is included at this point just preceding Table VIII.

TABLE VII Balt formation calculated on Condensate in turn derived frombasis of non-oxyalkylated Salt condensate from Salt conn- 37% Wt. of N 0. sate Amt. Amt. Amine formconden- Theo. 50% glu- N 0. Resin resin, Solvent sol- Amine used 1 used, aldesate on basic conic No. gms. vent, gms. hyde solventnitrogen, acid, gins, grns. free basis, grns. gins.

gms.

Amine 3 1, 518 53 1, 480 798 27 720 951 27 720 734 38 1, 065 773 38 1,065 826 38 1,065 847 42 1,175 886 42 1, 175 1,039 42 1, 175 880 42 1, 175 916 42 1, 175 1, 069 42 1, 175 1,518 21 720 734 19 535 880 21 585 1 For identification of amine numbers see ring compounds in Part Three. 2 30% formaldehyde. 8 See text following.

' TABLE VIII Grams of oxyalkylated compound Percent which is equiv. 50 percent Oxyalkylcondento grams of congluconic Ex. No. ated desate in densate acid to rivative, oxyalkylneutralex. N o. ated delze, grams Conden- Amt. con- EtO PrO Solvent rivative Oxyalkyl- Condensate, densate, amt amt, amt, ated comsate ex. No. lbs. lbs. lbs. lbs. pound 15. 18 6. 29. 4 5, 180 1, 518 1, 480 15. 18 6.0 22. 8 6, 700 1, 518 1, 480 15. 18 6.0 18. 6 8, 135 1, 518 1, 480 15. 46 4. 30. 5 2, 535 773 1, 065 15. 46 4. 5 23. 4 3, 300 773 1, 065 15. 46 4. 5 18. 9 4, 090 773 1, 065 15. 18 30. 3G 6. 0 29. 4 5, 180 l, 518 1, 480 15. 18 45. 54 6. 0 22. 8 6, 700 1, 518 1, 480 15.18 60. 72 e. o 18.6 1 8,185 1,518 ,480 15. 30. S2 4. 5 30. 5 2, 535 773 1, 065 15. 46 46. 38 4. 6 24. 5 3, 165 773 1, 065 15. 18 15, 1S 6. 0 22. 8 6, 700 1, 518 1, 480 15. 18 22. 77 6. 0 20. 7 7, 345 1, 518 1, 480 15. 18 30.36 0. 0 18. 6 8, 185 1, 518 1, 480 15. 46 108. 22 4. 5 9. 75 7, 740 773 535 15.46 108. 22 4. 5 9. 27 8, 0 773 535 PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of my process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifyingagents. Moreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oil-and water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of my invention when employed as demulsifying agents.

The materials of my invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953,. Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and. allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

Gluconic acid salt, for example, the product of Example 17, 20%;-

A cyclohexylamine salt of a polypropylated naphthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated naphthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%; p A high-boiling aromatic petroleum solvent, 15%;

27 Isopropyl alcohol, The above proportions are all weight percents.

PART 8 Also, the gluconic acid salts are useful in dry cleaners" soaps.

Also, they may be used as additives in connection with other emulsifying agents; they may be used to contribute hydrotropic effects; they may be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion particularly the corrosion of ferrous metals for various purposes and particularly in connection with the product of oil and gas, and also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or nonaqueous type; some have definite anti-corrosive action. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata and particularly in secondary recovery operations using aqueous flood waters.

After oxyalkylation a condensate of the kind previously described becomes a derivative which retains basic nitrogen radicals and also includes alkanol radicals such as the hydroxyethyl or hydroxypropyl radical. Thus, in attempting to dehydrate the oxyalkylated salt derivatives from gluconic acid or merely by heating there may be a rearrangement wherein one forms the ester in the same manner that triethanolamine oleate can be converted into oleyl triethanolamine. Thus the compounds described may serve as precursors for other derivatives obtained by esterification. In fact, any reference to decomposition on heating must of necessity include such possibility.

Having thus described my invention, what I claim as new and desire to obtain by Letters Patent is:

1. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forrning reactivity; said resin being derived by reaction between a difnnctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and 76 (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the threereactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom with a resin molecule; and with the further proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed bytthe third step of neutralizing with gluconic acid.

2. A three-step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial obsence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical havingat 7 least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic a-midines selectedfrom the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the molar ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

3. A three'step manufacturing process including the method of first condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said 1 phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2, 4, 6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule; by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

4. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunction-al only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2, 4, 6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule;

I with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alltylene oxide having not more than 4 carbon atoms and selected from the class consisting 30 of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

5. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 5 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a 'difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which. there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alphabeta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

6. A three-step manufacturing process including the method of first condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenol-formaldehyde resin havin which R is a para-substituted aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms; b) cyclic amidines selected from the class con- :sisting of substituted imidazolines and substituted tetrahyclropyrimidines in which there is present at least one basic secondary amino radical and characterized by freedom from any primary amino radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C. with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part tor" the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the molar ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by an oxyalkylation step by means of an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide; and followed by the third step of neutralizing with gluconic acid.

7. The manufacturing procedure of claim 1 wherein the oxyalkylation step is limited to the use of both ethyl ene oxide and propylene oxide in combination.

8. The manufacturing procedure of claim 2 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

32 9. The manufacturing procedure of claim 3 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

10. The manufacturing procedure of claim 4 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

11. The manufacturing procedure of claim 5 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

12. The manufacturing procedure of claim 6 wherein the oxyalkylation step is limited to the use of both ethylene oxide and propylene oxide in combination.

13. The product resulting from the three-step manufacturing procedure defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A THREE-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF FIRST CONDENSATING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULE WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING RE-ACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DICUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 